CN104555910B - A kind of method of preparing film ordered micro structure based on reactive ion beam etching technique - Google Patents
A kind of method of preparing film ordered micro structure based on reactive ion beam etching technique Download PDFInfo
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Abstract
Prepare a method for orderly Thinfilm pattern based on reactive ion etching polymer, belong to ordered micro structure technical field. Specifically the single polymer layer microballoon on substrate and surface thereof is carried out to reactive ion etching, thereby form orderly Thinfilm pattern at substrate surface, can regulate and control Thinfilm pattern by changing reactive ion etching parameter. Further carry out electroless deposition at this substrate surface again, metal nanoparticle can optionally be adsorbed on the region that there is no film or non-dense film, and then forms the oldered array of metal nanoparticle. The oldered array of metal nanoparticle has certain using value aspect Raman detection, plasma regulation and control. Meanwhile, because generated film surface has functional group, therefore can be applied to selective self assembly, and the selective absorption of enzyme, protein, aspect biological monitoring and sensing, also having reasonable application prospect.
Description
Technical field
The invention belongs to ordered micro structure technical field, be specifically related to one and prepare thin based on reactive ion etching polymerThe method of film ordered micro structure.
Background technology
Molecule is in the self assembly of substrate surface, refers to molecule spontaneous formation Thermodynamically stable, queueing discipline in substrateThe process of molecular film. The degree of order of molecular self-assembling depends primarily between molecule and substrate and between molecule and moleculeInteract. Group of molecules installs to suprabasil active force and mainly comprises physical absorption and chemisorbed, and physical absorption refers toHeat content is less than the effect of 10kcal/mol, and the interaction force between molecule and substrate is more weak, as Van der Waals force;Chemisorbed refers to that heat content is greater than the effect of 10kcal/mol, mainly comprises hydrogen bond, ion pair effect, covalent bond etc.Stronger active force, therefore chemisorption rate physical absorption is more stable.
1980, Sagiv reported first in oxide base self assembly organosilan film (J.AM.CHEM.SOC.1980,102:92～98); Nineteen eighty-three, Americanized scholar Nuzzo and Allara are by closing in two sulfurationsThe method of the adsorption in dilute solution of thing, has prepared fine and close mercaptan self-assembled film (J.AM.CHEM. in gold surfaceSOC.1983,105 (13): 4481～4483). No matter still wide in the degree of depth of research the structure of self-assembled film is with signAll there have been significant progress (CHEMREV.1996,96 (4): 1533～1554) in degree aspect.
Along with to deep the probing into of molecular self-assembling, people can utilize one-component or multicomponent to prepare self assemblyMembrane structure. The means of at present preparing patterning self-assembled film at substrate surface mainly comprise micro-contact printing technology, dip inWater-color paintbrush technology, solvent/heating self-organizing, electrochemistry desorption, etc. In a word, most of method needs first to basePatterning is carried out at the end, then carries out self assembly on the surface that has structure. As the people such as Jie-RenLi utilize colloid micro ball for mouldPlate, by the content of water at the bottom of control ball, utilizes octadecyl trichlorosilane alkane (OTS) self assembly to prepare nano-ringsAnd nanohole array (NanoLett.2008,8,7,1916～1922), after this, they are taking colloid micro ball as template,Modifying OTS without gear layer region, wash off after colloid micro ball, originally there iing the position modification organic sulfur class list of microballoon to divideSub-film, makes metal nanoparticle optionally be adsorbed on the long region (ACS that has organic mercaptan based monolayer filmNano.2009,3:2023～2035). The people such as WonmiAhn utilize colloid micro ball to do template, self assembly dimethyl twoChlorosilane, in conjunction with electroless deposition technique, Shi Jin island is optionally deposited on the region that does not have dimethyldichlorosilane to modify(ACSNano.2010,4:4181～4189)。
The existing Thinfilm pattern technical deficiency of preparing comprises following 2 points: need to introduce new material 1.; 2. conventionally utilizeA kind of template, is difficult to prepare multiple patterns.
Summary of the invention
The object of this invention is to provide a kind of method of preparing film ordered micro structure based on reactive ion etching polymer.Specifically to Tectonic but can etching, and the single polymer layer microballoon of substrate surface carries out reactive ion etching, fromAnd form orderly Thinfilm pattern at substrate surface, can regulate and control Thinfilm pattern by changing reactive ion etching parameter; SoAfter carry out electroless deposition at this substrate surface again, metal nanoparticle can optionally be adsorbed on does not have film or notThe region of dense film, and then the oldered array of formation metal nanoparticle.
The present invention propose the reactive ion etching technology that utilizes prepare the method for film ordered micro structure, concrete steps asUnder:
1, in silicon base, assemble polystyrene microsphere;
2, by reactive ion etching, the polystyrene microsphere in silicon base is carried out to etching;
3, utilize organic solvent to remove remaining polystyrene microsphere, thereby obtain polystyrene film at substrate surfaceOrdered micro structure.
In said method, what step 1 was mentioned assembles polystyrene microsphere in silicon base, comprises following several step:
(1) mixed solution of the second alcohol and water of preparation polystyrene microsphere (diameter 100～4000nm): by polyphenylEthene powder 0.1～1g joins in the water of 1～20mL, volume ratio 1:1 and the mixed solution of ethanol, and ultrasonic 1～6H, mixes it;
(2) cleaning silicon chip: by vollyball silicon chip with carry ball silicon chip and first use acetone, chloroform, second alcohol and water to exist successivelyUltrasonic cleaning 3～10min under 40～100W, then by NH3·H2O：H2O2：H2O volume ratio is 1～3:1～3:5～7 mixed solution is heated wash 50～70min at 80～100 DEG C, finally rinses with high purity water and blows with nitrogenDry, vollyball is positioned in surfactant stand-by;
(3) assembling of polystyrene microsphere monofilm and transfer: add high purity water in clean surface ware, and addMass fraction is the aqueous solution 20～100 μ L of 0.5～2% Surfactant SDS; Then use traceThe polystyrene microsphere solution that injector obtains step (1) is slowly added drop-wise on vollyball silicon chip, and along vollyball siliconSheet slips in water, makes it form the closelypacked polystyrene microsphere monofilm of six sides, then adds 5～25 of above-mentioned concentrationThe lauryl sodium sulfate aqueous solution of μ L makes monofilm stable; Then with carrying ball silicon chip, ball is mentioned, and slant settingUntil moisture volatilizees completely.
Polystyrene microsphere in the use reactive ion etching silicon base of mentioning in step 2, comprises the steps:
Carry ball silicon chip 5 × 10 by surface with polystyrene microsphere monofilm-5～8×10-5Under Pa vacuum, startEtching, the parameter of etching is: O2Flow is 5～70sccm, and chamber pressure is 10～90mtorr, and radio-frequency power is12～250w, ICP power is 30～300w, etch period is 1～9min.
In this course, substrate is activated, and the polystyrene material being etched away reacts generation in the process of being etchedWith the active material of free radical, this active material and substrate Cheng Jianhou deposit film forming in substrate; Due to surplus after etchingThe mask effect of remaining polystyrene microsphere, the region covering at original polystyrene microsphere does not have polystyrene filmExist.
The organic solvent that utilizes of mentioning in step 3 is removed remaining polystyrene microsphere, and concrete operation step is as follows:
The complete etching ball silicon chip of carrying is placed in toluene solution and soaks 0.5～1h, then super under 40～100w powerSound cleans 0.5～1h; Repeat immersion and ultrasonic cleaning process 5～10 times, finally use successively ethanol and high purity water to existUltrasonic cleaning 3～10min under 40～100w power, repeats this process 2～10 times, under AFM, observes,Until polystyrene microsphere is all cleaned.
In this process, only have polystyrene microsphere dissolved fall, expose the substrate below it; And deposit in substrateThe polystyrene film forming can not be removed, thereby the polystyrene film that deposition forms in substrate is had in orderMicro-structural.
On this basis, carry out electroless deposition on the ordered micro structure surface of above-mentioned polystyrene film, there is no filmOr the region of dense film does not obtain metal nanoparticle oldered array. The concrete steps of electroless deposition are as follows:
Preparation hydrofluoric acid, liquor argenti nitratis ophthalmicus (10-2Mol/L), the mixed solution of high purity water, volume ratio is 1～10:1～30:10～100, then put into above-mentioned mixed solution by the substrate of preparation in step 3, and deposition 1～5s, getsGo out rear fast with high purity water rinse, nitrogen dries up; Thereby obtain metal in the region that there is no film or non-dense filmNano particle ordered array.
In a word, taking polystyrene microsphere as mask plate, association reaction ion etching technology, makes to generate in etching processReactivity material and active substrate Cheng Jian, generate order thin film pattern, by changing etching parameters, can regulate and control figureCase shape, preparation as netted, alveolate texture, prepared film surface has functional group, can be used as electroless depositionOr the template of selective assembling, as obtained the oldered array of Nano silver grain by electroless deposition, and enzyme, proteinSelective absorption, aspect biological detection and sensing, also having reasonable application prospect.
Brief description of the drawings
Fig. 1: different Thinfilm patterns of the present invention construct schematic diagram;
Fig. 2: the SEM picture of application conditions 1 reactive ion etching polystyrene microsphere 1min and 2min, whereinFig. 2 (a1) and Fig. 2 (a2) represent respectively plane photo and the tangent plane photo of reactive ion etching 1min, Fig. 2 (b1)And Fig. 2 (b2) represent respectively plane photo and the tangent plane photo of reactive ion etching 2min;
Fig. 3: wash residue polyphenyl second after application conditions 1 reactive ion etching polystyrene microsphere 1min and 2min offAFM photo after alkene microballoon, wherein Fig. 3 (a1) and Fig. 3 (b1) represent respectively reactive ion etching 1min and 2After min, wash the height picture after residue polystyrene microsphere off, Fig. 3 (a2) and Fig. 3 (b2) respectively represent reaction fromAfter sub-etching 1min and 2min, wash the tangent plane of polystyrene microsphere off and analyze picture;
Fig. 4: the SEM picture of application conditions 2 reactive ion etching polystyrene microsphere 3min and 9min, whereinFig. 4 (a1) and Fig. 4 (a2) represent respectively plane picture and the tangent plane picture of reactive ion etching 3min, Fig. 4 (b1)And Fig. 4 (b2) represent respectively plane picture and the tangent plane picture of reactive ion etching 9min;
Fig. 5: wash residue polyphenyl second after application conditions 2 reactive ion etching polystyrene microsphere 3min and 9min offAFM picture after alkene microballoon, wherein Fig. 5 (a1) and Fig. 5 (b1) represent respectively reactive ion etching 3min and 9Min washes the height picture after residue polystyrene microsphere, Fig. 5 (a off2) and Fig. 5 (b2) represent respectively reactive ionEtching 3min and 9min, the tangent plane of washing off after residue polystyrene microsphere is analyzed picture;
Fig. 6: the SEM picture of application conditions 3 and condition 4 reactive ion etching polystyrene microsphere 1.5min, itsMiddle Fig. 6 (a1) and Fig. 6 (a2) while representing application conditions 3 respectively, after reactive ion etching polystyrene microspherePlane and sectional drawing, Fig. 6 (b1) and Fig. 6 (b2) while representing application conditions 4 respectively, reactive ion etching is poly-The plane of phenylethylene micro ball and sectional drawing;
Fig. 7: application conditions 3 and condition 4 reactive ion etching polystyrene microsphere 1.5min, wash residue polyphenyl offAFM picture after ethene microballoon, wherein Fig. 7 (a1) and Fig. 7 (b1) represent respectively application conditions 3 and condition 4Time, wash the height picture after residue polystyrene microsphere off, Fig. 7 (a2) and Fig. 7 (b2) represent respectively application barWhen part 3 and condition 4, the tangent plane of washing off after residue polystyrene microsphere is analyzed picture;
Fig. 8: application conditions 3 processing sample 1.5min, the AFM picture that the excessive rear scanning of degree of cleaning obtains;
Fig. 9: application conditions 1 reactive ion etching 1.5min washes the XPS spectrum figure of residue polystyrene microsphere test off;
Figure 10: application conditions 1 etching 2min washes residue polystyrene microsphere off, and electroless deposition 1～5s obtainsThe SEM picture of silver nanoparticle array; The sedimentation time of Figure 10 (a), (b), (c), (d), (e) correspondence dividesWei 1s, 2s, 3s, 4s and 5s.
Figure 11: application conditions 2 etching 3min wash residue polystyrene microsphere off, and electroless deposition 1～5s obtainsThe SEM picture of silver nanoparticle array; The sedimentation time of Figure 11 (a), (b), (c), (d), (e) correspondence dividesWei 1s, 2s, 3s, 4s and 5s.
Figure 12: application conditions: 3 etching 1.5min wash residue polystyrene microsphere off, and electroless deposition 1～5s obtainsThe SEM picture of silver nanoparticle array; The sedimentation time of Figure 12 (a), (b), (c), (d), (e) correspondence dividesWei 1s, 2s, 3s, 4s and 5s.
It shown in Fig. 1, is the schematic diagram of constructing of different self-organizing films. First the polyphenyl second that, we are 630nm by diameterAlkene microballoon is assembled in silicon chip surface and forms colloid monolayer ball array. In the time that application conditions 1 operates, in the pattern obtaining,1 place is the film that after reactive ion etching polystyrene microsphere, deposition forms in substrate, and 2 places are polystyrene microspheresPosition before washing, diameter is identical with the polystyrene diameter after etching, and 3 places are triangle spaces, have non-tightClose film forms; In the time that application conditions 2 operates, in the pattern obtaining, 4 places are before polystyrene microsphere washesPosition, diameter is identical with the polystyrene diameter after etching, and film deposits at 5 places; When application conditions 3 operatesTime, in the pattern obtaining, 6 places are films that deposition forms, and 7 places are residual polystyrene segments, and 8 places are threeSpace, angle, has non-tight film to form.
Shown in Fig. 2, be the SEM picture of the sample after reactive ion etching in embodiment 1 and embodiment 2, from figureCan find out, along with the prolongation of etch period, the diameter of ball diminishes, and shape becomes fusiformis by circle.
Shown in Fig. 3, be in embodiment 1 and embodiment 2, to wash the AFM picture after polystyrene microsphere off, fromIn figure, can find out, the cycle of the Thinfilm pattern forming on silicon chip is identical with the polystyrene microsphere cycle. And along withThe prolongation of etch period, the polystyrene spheres amount of being etched increases, and corresponding to 2 regions, place in Fig. 1, diameter is from 553.91Nm is reduced to 352.94nm, and film thickness is increased to 2.727nm from 2.244nm, and the above results explanation is passed throughChange size and thickness that etch period can regulate and control membrane structure.
Shown in Fig. 4, be the sample SEM picture after reactive ion etching in embodiment 3 and embodiment 4, can from figureTo find out, the isotropism of this condition etching is better than embodiment 1 and embodiment 2.
Shown in Fig. 5, be in embodiment 3 and embodiment 4, to wash the AFM figure scanning after polystyrene microsphere offSheet, as can be seen from the figure, the Thinfilm pattern of preparation is similar netted and cellular, its cycle and polystyrene microsphere weekPhase is identical, substrate generate film in Delta Region (corresponding to 5 regions, place of Fig. 1), under similarity condition, along withThe prolongation of time, middle border circular areas (4 regions, place of corresponding diagram 1) reduced, reduces from 583.32nmTo 367.64nm.
Shown in Fig. 6, be the SEM picture of the sample after reactive ion etching in embodiment 5 and embodiment 6, from figureCan find out, in the time that chamber pressure is 10mtorr, the etch rate of ball is accelerated greatly, and can from cross-sectional viewFind out, the shape of ball has become and has been similar to column, also further illustrates under this condition the effect ratio of inward collapsibleLarger, and in the time that chamber pressure is 50mtorr, the etch rate of ball obviously slows down, isotropism increases.
Shown in Fig. 7, be in embodiment 5 and embodiment 6, to wash the AFM figure scanning after polystyrene microsphere offSheet, as can be seen from the figure, when chamber pressure is 10mtorr, the sample of handling is washed polystyrene microsphere off, heightDisc area (6 regions, place of corresponding diagram 1) is out than the Delta Region subsiding (8 regions, place of corresponding diagram 1)About high 2.172nm, the interior ring diameter in intermediate annular hole (7 regions, place of corresponding diagram 1) is 68.626nm,Outer shroud is of a size of 254.90nm. When chamber pressure is 50mtorr, disc area exceeds with respect to middle border circular areasApproximately 2.369nm, middle border circular areas (being similar to 2 regions, place of Fig. 1) diameter is 436.37nm, bothContrast it seems, along with the increase of chamber pressure, Delta Region (being similar to 3 regions, place of Fig. 1) is with respect to disk districtThe difference in height in territory (being similar to 1 region, place of Fig. 1) is apart from reducing to some extent.
Shown in Fig. 8, be the AFM picture of sample degree of cleaning in embodiment 5 scanning when excessive, find to work asWhen degree of cleaning is excessive, the polystyrene molecule segment of the residual gathering of part is cleaned, but film is still retained inIn substrate.
Fig. 9 is that the sample in embodiment 7 carries out x-ray photoelectron power spectrum (XPS) and scans the spectrogram obtaining, itsMiddle Fig. 9 (a), Fig. 9 (b) and Fig. 9 (c) represent respectively the full spectrogram sheet that comprises all elements in sample, sampleIn carbon peak position (1 place's peak position in corresponding diagram 9 (a)) curve, and the 2p peak position curve of silicon. Fig. 9 (a)In 1 position, place in conjunction with being 284eV, represent sample with carbon, Fig. 9 (b) is to carbon in sampleTest the curve obtaining, the curve 2 in Fig. 9 (c) is with the origin software original spectrogram obtaining of mapping,Curve 3 is the matched curves that obtain curve 2 with XPSPEAK41 software, almost completely overlap, curve 4 beIn conjunction with the peak position curve that can punish out for 99.4eV, curve 5 is in the peak position in conjunction with can 99.9eV punishing outCurve, curve 6 is at the peak position curve of punishing out in conjunction with energy 104.4eV, wherein, the peak position pair at 99.4eV placeWhat answer is the peak position of silicon, and what peak position corresponding to 99.9eV place was corresponding is the peak position of silicon and phenyl ring Cheng Jian, 104.4eV placeCorresponding peak position is the peak position that the material of the current 4 valency silicon of not yet probing into out forms.
Figure 10 is embodiment 9, embodiment 10, embodiment 11, embodiment 12, the SEM of embodiment 13 gainedPicture can be found out from SEM picture, and in the time that sedimentation time is 1s, Nano silver grain is first in centerPlace's deposition, herein corresponding to 2 regions in Fig. 1, reason may be there is no barrier layer herein, makes Nano silver grain excellentFirst deposit herein, in the time that sedimentation time extends to 3s, Nano silver grain continues deposition herein, works as time lengtheningTo 4s, when 5s, Nano silver grain starts in 2 regions with external sediment, but due to the existence on barrier layer, and everyThe density difference at one place, makes the no longer particularly compact of deposition of Nano silver grain.
Figure 11 is embodiment 14, embodiment 15, embodiment 16, embodiment 17, the SEM of embodiment 18 gainedPicture can be found out from SEM picture, with the Nano silver grain of the substrate deposition of this net-like pattern ratio of arrangingMore even, do not present the high feature of zone line Nano silver grain bulk density, owing to obtaining under this kind of etching conditionPatterned substrate, angular position, corresponding to 5 in Fig. 1, barrier layer is dense, so prolonging along with the timeLong, Nano silver grain can, at zone line, corresponding to 4 places in Fig. 1, continue deposition, even and if in Figure 10The same time 5s of sample deposition, what Delta Region also can be obvious reserved by sky comes.
Figure 12 is embodiment 19, embodiment 20, embodiment 21, embodiment 22, the SEM of embodiment 23 gainedPicture, can find out from SEM picture, in the time that sedimentation time is 1～2s, Nano silver grain is preferentially adsorbed on figureThe center position in 7 regions in 1, along with the prolongation of time, in the time that sedimentation time is 3s, Nano silver grain depositionStart 6 and 7 centre position, region depositions in Fig. 1, in the time that sedimentation time is 4s, Nano silver grain is just openedBegin in other local depositions, in the time that sedimentation time is 5s, the deposition of other positions obviously increases, but polyphenyl secondAlkene segment (7 regions in Fig. 1) locates not have deposition always.
Detailed description of the invention
Further illustrate the inventive method and application below by embodiment, instead of limit with these embodimentThe present invention. The present invention has mainly adopted polystyrene microsphere, utilizes reactive ion etching technology, and reaction is generatedActive material and substrate Cheng Jian, form and have optionally Thinfilm pattern, realizes the ordered structure of Nano silver grain and construct.Equally also can apply other ordered polymers, association reaction ion etching technology, prepares regularly arranged self-organizing film,This has film optionally and also can be widely used in other the constructing of Metallic Microstructure, and protein and enzymeSome biological detection such as absorption and bio-sensing aspect.
Embodiment 1-7
The cavity of the silicon chip that sequences polystyrene microsphere being put into reactive ion etching machine, vacuumizes, and works as pressureReach 7.26 × 10-5When Pa, the program operation of parameter will be editted. The parameter setting is as follows:
Embodiment 1: condition 1 etching 1min; Embodiment 2: condition 1 etching 2min;
Embodiment 3: condition 2 etching 3min; Embodiment 4: condition 2 etching 9min;
Embodiment 5: condition 3 etching 1.5min; Embodiment 6: condition 4 etching 1.5min;
Embodiment 7: condition 1 etching 1.5min;
Clean polystyrene microsphere with toluene solvant, carry out during this time atomic force microscope observation, wash until observeTill polystyrene spheres.
Table 1: the corresponding parameter of each etching condition
| Condition | Gas flow/sccm | Chamber pressure/mtorr | Radio-frequency power/w | ICP/w |
| 1 | 50 | 30 | 200 | 200 |
| 2 | 50 | 30 | 12 | 200 |
| 3 | 50 | 10 | 200 | 200 |
| 4 | 50 | 50 | 200 | 200 |
Embodiment 8
By four probe method to blank silicon chip, embodiment 2, embodiment 3, embodiment 5 carries out the measurement of square resistance.To survey data as follows:
Table 2: the square resistance data of each embodiment product
| Sample | Blank silicon chip | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Resistance value/Ω | 138 | 140.4 | 143.6 | 144.2 |
Embodiment 9
Hydrofluoric acid is put in the substrate that embodiment 2 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity water=1:3.5:18In (volume ratio), after 1s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 10
Hydrofluoric acid is put in the substrate that embodiment 2 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 2s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 11
Hydrofluoric acid is put in the substrate that embodiment 2 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 3s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 12
Hydrofluoric acid is put in the substrate that embodiment 2 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 4s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 13
Hydrofluoric acid is put in the substrate that embodiment 2 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 5s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 14
Hydrofluoric acid is put in the substrate that embodiment 3 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 1s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 15
Hydrofluoric acid is put in the substrate that embodiment 3 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 2s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 16
Hydrofluoric acid is put in the substrate that embodiment 3 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 3s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 17
Hydrofluoric acid is put in the substrate that embodiment 3 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 4s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 18
Hydrofluoric acid is put in the substrate that embodiment 3 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 5s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 19
Hydrofluoric acid is put in the substrate that embodiment 5 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity water=1:In 3.5:18 (volume ratio), after 1s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 20
Hydrofluoric acid is put in the substrate that embodiment 5 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 2s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 21
Hydrofluoric acid is put in the substrate that embodiment 5 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 3s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 22
Hydrofluoric acid is put in the substrate that embodiment 5 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 4s, take out, large water gaging rinses, and nitrogen dries up.
Embodiment 23
Hydrofluoric acid is put in the substrate that embodiment 5 is handled well: liquor argenti nitratis ophthalmicus (10-2Mol/L): high purity waterIn=1:3.5:18 (volume ratio), after 5s, take out, large water gaging rinses, and nitrogen dries up.
Claims (4)
1. utilize reactive ion etching technology to prepare a method for film ordered micro structure, its step is as follows:
1) in silicon base, assemble polystyrene microsphere;
2) by reactive ion etching, the polystyrene microsphere in silicon base is carried out to etching;
3) utilize organic solvent to remove remaining polystyrene microsphere, thereby obtain polystyrene at substrate surfaceThe ordered micro structure of film;
Step 1) mention in silicon base, assemble polystyrene microsphere, comprise following several step:
(1) mixed solution of the second alcohol and water of preparation polystyrene microsphere: by Polystyrene powder 0.1～1gJoin in the water of 1～20mL, volume ratio 1:1 and the mixed solution of ethanol, ultrasonic 1～6h,It is mixed;
(2) cleaning silicon chip: by vollyball silicon chip with carry ball silicon chip and first use acetone, chloroform, second alcohol and water successivelyUltrasonic cleaning 3～10min under 40～100w, then by NH3·H2O：H2O2：H2O bodyThe mixed solution that long-pending ratio is 1～3:1～3:5～7 heated wash 50～70 at 80～100 DEG CMin, finally rinses with high purity water and dries up with nitrogen, is positioned in surfactant stand-by;
(3) assembling of polystyrene microsphere monofilm and transfer: in clean surface ware, add high purity water, andAdding mass fraction is the aqueous solution of 0.5～2% Surfactant SDS20～100 μ L; Then the slowly row of being added drop-wise to of polystyrene microsphere solution step (1) being obtainedOn ball silicon chip, and slip in water along vollyball silicon chip, make it form the closelypacked polyphenyl of six sidesEthene microballoon monofilm, then add the lauryl sodium sulfate of 5～25 μ L of above-mentioned concentration water-solubleLiquid makes monofilm stable; Then with carrying ball silicon chip, ball is mentioned, and slant setting is until moisture is completeFull volatilization, realizes and in silicon base, assembles polystyrene microsphere;
Step 2) in polystyrene microsphere in the use reactive ion etching silicon base mentioned, be by surface withPolystyrene microsphere monofilm carry ball silicon chip 5 × 10-5～8×10-5Under Pa vacuum, start etching;O2Flow is 5～70sccm, and chamber pressure is 10～90mtorr, and radio-frequency power is 12～250w,ICP power is 30～300w, and etch period is 1～9min.
2. a kind of side that utilizes reactive ion etching technology to prepare film ordered micro structure as claimed in claim 1Method, is characterized in that: step 3) in the organic solvent that utilizes mentioned remove remaining polystyrene microsphere,Be that the complete reactive ion etching ball silicon chip of carrying is placed in toluene solution and soaks 0.5～1h, then existUltrasonic cleaning 0.5～1h under 40～100w power; Repeat immersion and ultrasonic cleaning process 5～10 times,Finally use successively ethanol and high purity water ultrasonic cleaning 3～10min under 40～100w power, repeat thisProcess 2～10 times, until observe until polystyrene microsphere is all cleaned under AFMTill.
3. a kind of side that utilizes reactive ion etching technology to prepare film ordered micro structure as claimed in claim 1Method, is characterized in that: further carry out nothing electricity on the polystyrene film ordered micro structure surface obtainingDeposition, thus the orderly battle array of metal nanoparticle obtained in the region that there is no film or non-dense filmRow.
4. a kind of side that utilizes reactive ion etching technology to prepare film ordered micro structure as claimed in claim 3Method, is characterized in that: electroless deposition is that the mixing of preparation hydrofluoric acid, liquor argenti nitratis ophthalmicus and high purity water is moltenLiquid, volume ratio is 1～10:1～30:10～100, then surface is had to polystyrene film orderlyAbove-mentioned mixed solution is put in the substrate of micro-structural, and electroless deposition 1～5s uses high purity water fast after taking-upRinse, nitrogen dries up.
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| CN107416765A (en) * | 2017-06-20 | 2017-12-01 | 苏州大学 | The method that nano concavo-convex structure is formed in plane or curved surface |
| CN108982464A (en) * | 2018-04-17 | 2018-12-11 | 中国科学院合肥物质科学研究院 | A kind of high distribution density nano gap oldered array and the preparation method and application thereof |
| CN108996469A (en) * | 2018-07-27 | 2018-12-14 | 纤瑟(天津)新材料科技有限公司 | A kind of silicon substrate of the production method and application of nano-hole golden the film film |
| CN110261951A (en) * | 2019-07-04 | 2019-09-20 | 南开大学 | High performance surface enhances the circular polarization dichroics and method of chiral optic response |
| CN110850017B (en) * | 2019-11-25 | 2020-08-18 | 中国计量科学研究院 | Method for accurately quantifying C peptide in serum without derivatization for non-disease diagnosis purpose |
| CN112599611B (en) * | 2020-12-14 | 2022-08-30 | 苏州大学 | Method for preparing photoelectric detector with wavelength selective response |
| CN115894079B (en) * | 2022-11-14 | 2024-01-26 | 季华实验室 | Polystyrene microsphere membrane and preparation method and application thereof |
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| CN101382734A (en) * | 2008-10-23 | 2009-03-11 | 中国科学院光电技术研究所 | Method for making nano lens array |
| CN101497429A (en) * | 2009-03-06 | 2009-08-05 | 吉林大学 | Method for preparing silicon hollow nano-cone array |
| CN102321905A (en) * | 2011-10-10 | 2012-01-18 | 吉林大学 | Method for preparing multilevel-structure alumina by pattern prefabrication through micro-nano ball arrangement |
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| CN101382734A (en) * | 2008-10-23 | 2009-03-11 | 中国科学院光电技术研究所 | Method for making nano lens array |
| CN101497429A (en) * | 2009-03-06 | 2009-08-05 | 吉林大学 | Method for preparing silicon hollow nano-cone array |
| CN102321905A (en) * | 2011-10-10 | 2012-01-18 | 吉林大学 | Method for preparing multilevel-structure alumina by pattern prefabrication through micro-nano ball arrangement |
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